(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-1-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七-12,16-二烯-5-酮合成路线 （共 52 条）
→
193146-53-1(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-1-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七-12,16-二烯-5-酮
反应条件
1.1: 18-crown-6; KHMDS / tetrahydrofuran / 1 h / -78 °C 1.2: 93 percent / tetrahydrofuran / 1 h / -78 °C 2.1: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C 3.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C 4.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C 5.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C 5.2: tetrahydrofuran / 1.5 h / -95 - -80 °C 6.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C 7.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Tetrahedron Letters, 1998 , vol. 39, # 47 p. 8633 - 8636
→
193146-53-1(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-1-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七-12,16-二烯-5-酮
反应条件
1.1: Ph3P; imidazole; I2 / acetonitrile; diethyl ether / 1 h / 20 °C 2.1: 18-crown-6; KHMDS / tetrahydrofuran / 1 h / -78 °C 2.2: 93 percent / tetrahydrofuran / 1 h / -78 °C 3.1: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C 4.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C 5.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C 6.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C 6.2: tetrahydrofuran / 1.5 h / -95 - -80 °C 7.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C 8.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Tetrahedron Letters, 1998 , vol. 39, # 47 p. 8633 - 8636
→
193146-53-1(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-1-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七-12,16-二烯-5-酮
反应条件
1.1: 98 percent / DIBALH / tetrahydrofuran; heptane / 2.5 h / 0 °C 2.1: Ph3P; imidazole; I2 / acetonitrile; diethyl ether / 1 h / 20 °C 3.1: 18-crown-6; KHMDS / tetrahydrofuran / 1 h / -78 °C 3.2: 93 percent / tetrahydrofuran / 1 h / -78 °C 4.1: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C 5.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C 6.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C 7.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C 7.2: tetrahydrofuran / 1.5 h / -95 - -80 °C 8.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C 9.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Tetrahedron Letters, 1998 , vol. 39, # 47 p. 8633 - 8636
→
193146-53-1(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-1-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七-12,16-二烯-5-酮
反应条件
1.1: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C 2.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C 3.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C 4.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C 4.2: tetrahydrofuran / 1.5 h / -95 - -80 °C 5.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C 6.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Tetrahedron Letters, 1998 , vol. 39, # 47 p. 8633 - 8636
→
193146-53-1(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-1-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七-12,16-二烯-5-酮
反应条件
1.1: 97 percent / benzene / 8 h / Heating 2.1: 10.95 g / LiHMDS / tetrahydrofuran / 0.67 h / 55 °C 3.1: oxalyl chloride; DMSO; DIPEA / CH2Cl2 / -78 - 20 °C 4.1: KHMDS; 18-crown-6 / tetrahydrofuran / 0.25 h 4.2: 5.45 g / tetrahydrofuran / 0.5 h / -78 °C 5.1: 98 percent / DIBALH / tetrahydrofuran; heptane / 2.5 h / 0 °C 6.1: Ph3P; imidazole; I2 / acetonitrile; diethyl ether / 1 h / 20 °C 7.1: 18-crown-6; KHMDS / tetrahydrofuran / 1 h / -78 °C 7.2: 93 percent / tetrahydrofuran / 1 h / -78 °C 8.1: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C 9.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C 10.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C 11.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C 11.2: tetrahydrofuran / 1.5 h / -95 - -80 °C 12.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C 13.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
→
193146-53-1(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-1-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七-12,16-二烯-5-酮
反应条件
1.1: 99 percent / imidazole / dimethylformamide / 3 h / 0 - 20 °C 2.1: 18-crown-6; KHMDS / tetrahydrofuran / 1 h / -78 °C 2.2: 93 percent / tetrahydrofuran / 1 h / -78 °C 3.1: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C 4.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C 5.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C 6.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C 6.2: tetrahydrofuran / 1.5 h / -95 - -80 °C 7.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C 8.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
→
193146-53-1(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-1-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七-12,16-二烯-5-酮
反应条件
1.1: 99 percent / Dess-Martin periodinane; Py / CH2Cl2 / 2 h / 0 °C 2.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C 2.2: tetrahydrofuran / 1.5 h / -95 - -80 °C 3.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C 4.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
→
193146-53-1(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-1-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七-12,16-二烯-5-酮
反应条件
1.1: 88 percent / TBAF / tetrahydrofuran / 10 h / 20 °C 2.1: 99 percent / imidazole / dimethylformamide / 3 h / 0 - 20 °C 3.1: 18-crown-6; KHMDS / tetrahydrofuran / 1 h / -78 °C 3.2: 93 percent / tetrahydrofuran / 1 h / -78 °C 4.1: 65 percent / Na2HPO4; Na-Hg amalgam / methanol; tetrahydrofuran / -15 - 20 °C 5.1: 99 percent / CSA / methanol; CH2Cl2 / 5 h / 0 - 10 °C 6.1: Dess-Martin periodinane; pyridine / CH2Cl2 / 4 h / 20 °C 7.1: LDA / tetrahydrofuran / 1 h / -78 - -35 °C 7.2: tetrahydrofuran / 1.5 h / -95 - -80 °C 8.1: 99 percent / 2,6-lutidine / CH2Cl2 / 3 h / 0 °C 9.1: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Journal of Organic Chemistry, 2000 , vol. 65, # 22 p. 7456 - 7467
→
193146-53-1(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-1-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七-12,16-二烯-5-酮
反应条件
1: N-Tos-D-valine, BH3*THF / CH2Cl2 / 4 h / -78 °C 2: 99 percent / 2,6-lutidine / CH2Cl2 / 2 h / 0 °C 3: 2,6-lutidine / CH2Cl2 / 3 h / 0 °C 4: 87 percent / CSA / methanol; CH2Cl2 / 4 h / 0 °C View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Tetrahedron Letters, 1998 , vol. 39, # 47 p. 8633 - 8636
193146-53-1(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-三-{[叔-丁基(二甲基)硅烷基]氧基}-1-羟基-4,4,6,8,12,16-六甲基-17-(2-甲基-1,3-噻唑-4-基)十七-12,16-二烯-5-酮
→
反应条件
1.1: PCC 1.2: 90 percent / NaClO2 2.1: 73 percent / TBAF 3.1: 77 percent / TCBCl; DIEA; DMAP 4.1: 59 percent / HF*pyr 5.1: 65 percent / mCPBA View Scheme
参考文献
Mulzer, Johann; Mantoulidis, Andreas; Oehler, Elisabeth
Tetrahedron Letters, 1998 , vol. 39, # 47 p. 8633 - 8636
